Photographic silver halide materials utilizing succinmonoamido benzoyl acetanilide color couplers



Sept.

12, 1967 sHlRo KIMURA ETAL PHOTOGRAPHIC SILVER HALIDE MATERIALSUTILIZING SUCCINMONOAMIDO BENZOYL ACETANILIDE COLOR COUPLERS Filed Maren2s, 1964 DYES MADE FROM: 4

Y cooH l. c.6H33cH=cHHcoHNQcocHZcoHN 3 cHzcooH ocH3 cooH 2.c|6H33cH=cHHCoHNQcocHzcoHNQ cHzcooH ocQHs cooH s. cH35c0HNOc0cH2coHNCcooH WAVELENGTH IN MILLIMICRONS INVENTORS im u r a Shir-O ing thecarboxyl group or groups A caboxyl or sulfonic United States PatentOiiice ABSTRACT OF THE DISCLOSURE A yellow-forming component or colorcoupler for silver halide emulsions used in light-sensitive colorphotography having the following general formula CO CHnC ON H- RCH=CHCHCON E@ OR OHiCOOH COOH wherein R is an alkyl group having 8-16 carbonatoms and R is an alkyl group having l-4 carbon atoms. The coupler showsa sutcient solubility in aqueous media and a suitable spectraladsorption for color photography.

` The presentv invention relates generally to a photograph- .icsensitivematerial containing a yellow couplerhaving the general formulaCOOH COCHZCONI-I- t i OR.

CHzCOOH wherein R is an alkyl group having 8-716 carbon atoms "and R isan alkyl group having 1 4 carbon atoms.

. Conventional yellow couplers for a subtractive color process arederivatives of lt-keto acid, which have in the molecules at least onecarboxyl group or sulfonic acid group as an alkali-soluble group i.e., agroup solubilizing the molecule in alkaline media. The alkali-solublegroups of these known derivatives, that is, the carboxyl groups orsulfonic acid groups are ones attached to the benzene nucleus of ananilide or the side chain of a benzoyl nucleus, but Vmost o f them areones attachedto the atomic group of one side of an active methylenegroup.

A coupler which has been usedhitherto has a carboxyl group or carboxylgroups but in the known coupler havatonly one side of the activemethylene group, the solubility in an alkali of the coupler cannot beimproved remarkably by increasing the number of carboxyl groups. Hence,`it frequently occurs that the coupler is precipitated when added to anemulsion or even precipitated in an after-treatment step from aphotographic sensitive material containing the coupler, which results inreducing markedly the transparency of the image.

Further, when a coupler is used in which at least one acid group isintroduced into the benzene nucleus of -keto acid anilde, not only isthe absorption spectrum of thus formed pigment shifted to the longerwave length side of the spectrum but valso the absorption in greenregions of the spectrum is broadened, which adversely aects the colorreproduction.

Therefore, an object of this invention is to provide a photographicsensitive material containing a yellow coupler having good solubility.

Another object of this invention is to provide a color 3,341,331Patented Sept. 12, 1967 photographic sensitive material having goodcolor reproducing property.

A further object of this invention is to provide a color photographicsensitive material which does not have such drawbacks as mentionedabove.

The coupler employed in this invention contains hydrophilic carboxylgroups in both groups attached to an active methylene group and has veryhigh solubility in an alkali as compared with a conventional couplercontaining one or more alkali-soluble groups in only one of the groupsattached to the active methylene group. Therefore, the coupler in thisinvention is not precipitated when it is added in an emulsion or is notprecipitated in an after-treatment step, thereby allowing a color imagehaving excellent transparency to be obtained.

While the absorption spectrum of a pigment shifts always toward thelonger wave side of the spectrum when a coupler which contains anelectron attractive group such as carboxyl group is used, the absorptionspectrum of a pigment does not shift toward the longer wave side and themaximum absorption wave length is narrow when the coupler according tothis invention is used. Accordingly, the absorption in the green regionwhich adversely affects the color reproduction is very small when thecouplers of this invention are employed.

Moreover, the color image obtained from the coupler according to thisinvention has `a very excellent durability against the eiect oftemperature, humidity and light.

As described above, a natural color image of excellent colorreproduction can be obtained when the couplers according to thisinvention-is used.

Examples of the couplers according to this invention are: l

/COOH -COCHZCOHNQ o ou,

(Il) S-carboxy-Z-methoxy-(4-tetradecenylsuccinmonoamido) benzoylacetanilide,

COOH

l -oocmooHN-O (III)5-carboxy-2-ethoxy-(4-octadecenylsuccinmonoamido)benzoyl acetanilide,

oooH

-oooHlooHN-O CH2() 0 OH I COCHaC OHN CHzCOOH 1. SYNTHESIS OF CARBOXY 2METHOXY- (4 OCTADECENYLSUCCINMONOAMIDO)BEN- ZOYL ACETANILIDE One mole of5-carboxy-2-methoxy-(4-aminobenzoyl) acetanilide and 1 mole ofoctadecenyl succinic anhydride .are put in a three neck ask, one literof dimethyl formaldehyde is added, and they are heated to 95 C. withstirring and reacted at that temperature for 4 hrs. After reaction, theproduct is cooled to normal temperature, poured in 7 liters of ice waterto deposit crystals. It is filtered under suction, washed well withwater, and dried. On recrystallizing from methanol, the above-identifiedacetanilide which decomposes at G-159 C. is obtained.

Yield: 60%.

2. SYNTHESIS OF 5 CARBOXY 2 METHOXY- (4-TETRADECENYLSUCCINMONOAMIDO BEN-ZOYL ACETANILIDE To 1 mole of 5-carboxy-2-methoxy-(4-aminobenzoyl)acetanilide and l mole of tetradecenyl succinic anhydride is added 1liter of dimethyl formaldehyde and they are treated as described in l.The above-identified acetanilide which melts at 15S-156 C. is obtained.

Yield: 60%.

3. SYNTHESIS OF 5 CARBOXY 2 ETHOXY- (4 OCTADECENYLSUCCINMONOAMIDO)BEN-ZOYL ACETANILIDE To 1 mole of 5-carboxy-2-ethoxy- (4-aminobenzoyl)acetanilide and 1 mole of octadecenyl succinic anhydride is added 1liter of dimethyl formaldehyde and they are treated as described in l.The above-identified acetanilide which melts at 163-165 C. is obtained.

Yield: 65%.

The use of the couplers is further illustrated by the followingexamples.

Example 1 200 ml. of an aqueous 5% alkali solution (3.5 ml. of onenormal solution -of caustic soda is used per one gramme of coupler) of5-carboxy-2-methoxy(4-octadecenylsuccinrnonoamido)benzoyl acetanilide(Formula I) is mixed with 1 kg. of a silver halide photographic emulsionand the pH of the solution is adjusted to 7.1-8.0 with caustic soda orcitric acid. The mixture is applied on a support such as film, dried,developed with the following developer after exposure, bleached andfixed.

l G. N,Ndiethyl par-aphenylene diamine 2.0 Sodium sulte 2.0 Sodiumcarbonate 20.0 Potassium bromide Balance water to make l liter.

The yellow image so obtained has its maximum absorption at 440 ma, hightransparency and excellent light fastness, and is decolored very littleby the effect of temperature and humidity.

Example 2 In .place of the coupler of Formula I in Example l, 5 carboxy2 methoxy (4 tetradecenylsuccinmonoamido)benzoyl acetanilide (FormulaII) is used and treated as described in Example l.

The yellow image so obtained has its maximum absorption at 440 ma, hightransparency and suitable hue.

Example 3 In place of the coupler of Formula I in Example 1, 5 carboxy 2ethoxy (4 octadecenylsuccinmonoamido)benzoyl acetanilide (Formula III)is used and treated as desecribed in Example l.

The yellow image so obtained has its maximum absorption at 441 ma, hightransparency, land the sharpness 22 ml. of an aqueous 5% alkali solution(3.4 ml. of one normal solution of caustic soda is used per one grammeof coupler) of 3.5-dicarboxy-(4-stearoylmonoamido)benzoyl acetanilide(the comparative coupler) is mixed with g. of the silver halidephotographic emulsion used in Example 1, adjusted to the pH value of7.1- 8.0 with caustic soda or citric acid. The mixture is coated on asupport such as lm, dried, then treated as described in Example l.

The yellow image so obtained has its maximum absorption at 445 mp., andthe absorption in the green region which affects the color reproductionis larger than the absorption obtained from the coupler according tothis invention.

In the drawing are shown absorption curves 1, 2 and 3 of dyes obtainedby development of a silver halide emulsion with aN,Ndiethylparaphenylene diamine in the presence of the compounds ofFormulas I, and III and the comparative coupler having the structureshown in the legend of the drawing. The spectroscopic absorption curvesobtained by the normalized maximum absorption of visible region areused. The maximum absorption obtained with couplers of Formulas I, II,III, and the comparative coupler of Example 4 are also shown in thefollowing table.

Formula: Maximum absorption, mp. I 440 II 440 III 441 Comparativecoupler 445 In the next table are shown the degradative ratio of bluefilter density resulting from the exposure of the yellow imagecontaining the indicated couplers for 7 days at 50 C., 90% relativehumidity.

In the next table are shown the degradative ratio of blue filter densityresulting from the exposure of the yellow image containing the indicatedcouplers for l2 hours by Xenon-tester (Shimazu XF-20 type).

Formula: Degradative ratio, percent I 43' II 42 III v 40 Comparativecoupler 53 wherein R is an alkyl group having 8-16 carbon atoms and R'is an alkyl group having 1-4 carbon atoms.

2. The photographic sensitive material as claimed in claim 1 whereinsaid coupler is 5carboxy2methoxy(4 octadecenylsuccinmonoamido)benzoylacetanilide.

3. The photographic sensitive material as claimed in claim 1 whereinsaid coupler is 5carboXy2methoXy-(4 tetradecenylsuccinmonoamido) benzoylacetanilide.

4. The photographic sensitive material as claimed in claim 1 whereinsaid coupler is 5-carboxy-2-ethoxy-(4-ootadecenylsuccinmonoamido)benzoylacetanilide.

5. The photographic sensitive material as claimed in claim 1 whereinsaid coupler is S-carboxy-Z-methoxy-(3-octadecenylsuccinmonoamido)benzoyl acetanilide.

6. The photographic sensitive material as claimed in claim 1 whereinsaid coupler is S-carboxy-Z-methoXy-(4- dodecenylsuccinmonoamido)benzoyl acetanilide.

7. A light sensitive silver halide photographic emulsion containing anon-diffusing coupler compound of the general formula OR CHICOOH COOHOR' CHzC 0 OH wherein R is an alkyl group having 8-16 carbon atoms and Ris an alkyl group having 1-4 carbon atoms.

References Cited UNITED STATES PATENTS 3,056,674 10/ 1962 Hofstadt etal.

I. TRAVIS BROWN, Primary Examiner. NORMAN G. TORCHIN, Examiner.

8. THE PROCESS OF PRODUCING A YELLOW DYESTUFF IMAGE IN A SILVER HALIDE EMULSION WHICH COMPRISES EXPOSING SAID EMULSION TO LIGHT AND DEVELOPING THE SAME WITH A PRIMARY AROMATIC AMINO DEVELOPER IN THE PRESENCE OF A 